An expansion method for calculating atomic properties IV. Transition probabilities

Abstract

An earlier expression for the expectation value of a single-electron operator which isstationary with respect to first-order variations of the state wave function has been generalized to the case of an off-diagonal matrix element connecting two different states. Explicit calculations are carried out of the probabilities of dipole transitions between configurations 1 s a 2 s b 2 p c and 1 s a 2 s b–1 2 p c+1 for all members of the isoelectronic sequences from helium to neon and the importance of taking into account the mixing of degenerate configurations is demonstrated. The accuracy is at least comparable to that of the Hartree-Fock approximation and in cases where degeneracy is important it is much superior.